Acylcyclohexanediones and the oxime ethers thereof with herbicidal and plant growth regulating properties

ABSTRACT

The invention relates to novel 2-acyl-1,3-cyclohexanediones and the oxime ethers thereof with herbicidal and plant growth regulating properties. 
     The novel 2-acyl-1,3-cyclohexanediones and the oxime ethers thereof are of the formula I ##STR1## wherein A is a 2- or 7-membered alkylene bridge, or a 3- to 7-membered alkenylene bridge which may be mono- or polyunsaturated, 
     n is 0, 1 or 2, 
     R 1  is C 1  -C 4  alkyl or benzyl, 
     R 2  is C 1  -C 6  alkyl which is unsubstituted or substituted by halogen, C 1  -C 4  alkoxy or C 1  -C 4  alkylthio; or is C 3  -C 6  cycloalkyl; or phenyl, benzyl or phenylethyl, the phenyl ring of each of which may be substituted by ahlogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, C 1  -C 4  alkylthio, C 1  -C 4  haloalkyl, C 1  -C 4  haloalkoxy, cyano or nitro, 
     X is oxygen or a radical --NOR 3 , and 
     R 3  is C 1  -C 6  alkyl, C 1  -C 6  haloalkyl, C 3  -C 6  alkenyl, C 3  -C 6  haloalkenyl or C 3  -C 6  alkynyl and to the metal and quaternary ammonium salts of these compounds. 
     The invention also relates to processes for the preparation of these acylcyclohexanediones and of the oxime ethers thereof, as well as to novel intermediates.

The present invention relates to novel 2-acyl-1,3-cyclohexanediones andthe oxime ethers thereof with herbicidal and plant growth regulatingproperties, to the preparation of said 2-acyl-1,3-cyclohexanediones andof the oxime ethers thereof, to compositions containing these novelsubstances and also to the use of said substances or of compositionscontaining them for controlling weeds and for regulating plant growth.

The novel 2-acyl-1,3-cyclohexanediones and the oxime ethers thereof areof the formula I ##STR2## wherein A is a 2- to 7-membered alkylenebridge, or a 3-to 7-membered alkenylene bridge which may be mono- orpolyunsaturated,

n is 0, 1 or 2,

R₁ is C₁ -C₄ alkyl or benzyl,

R₂ is C₁ -C₆ alkyl which is unsubstituted or substituted by halogen, C₁-C₄ alkoxy or C₁ -C₄ alkylthio; or is C₃ -C₆ cycloalkyl; or phenyl,benzyl or phenylethyl, the phenyl ring of each of which may besubstituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio,C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, cyano or nitro,

X is oxygen or a radical --NOR₃, and

R₃ is C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₃ -C₆ alkenyl, C₃ -C₆ haloalkenylor C₃ -C₆ alkynyl.

The invention also relates to the isomers, enantiomers anddiastereo-isomers of the compounds of formula I, as well as to the saltsof said compounds with metals and quaternary ammonium bases.

In the above definitions alkyl by itself or as moiety of anothersubstituent such as alkoxy, alkylthio, haloalkyl or haloalkylthio shallbe understood as comprising straight chain and branched radicals, e.g.methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, as well as all stereosiomers of the higher homologues.Alkenyl and alkynyl also comprise straight chain and branched radicals,as well as the cis- and trans-forms thereof, e.g. allyl, methallyl,butenyl, methylbutenyl, dimethylbutenyl, ethynyl, propynyl, butynyl,methylbutynyl, dimethylbutynyl.

Cycloalkyl radicals R₂ or cycloalkyl radicals which are formed by thecarbon atom and the alkylene bridge A comprise cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Cycloalkenyleneradicals formed by the carbon atom and the alkenylene bridge A may bemono- or polyunsaturated, e.g. cyclopropenyl, cyclobutenyl,cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl,cycloheptenyl, cycloheptadienyl, cycloheptatrienyl, cyclooctenyl,cyclooctadienyl and cyclooctatrienyl. These radicals may be substitutedby up to 5 methyl groups.

Halogen shall be understood as meaning fluorine, chlorine, bromine oriodine atoms.

The 2-acyl-1,3-cyclohexanediones, and the oxime ethers thereof, offormula I are distinguished by good herbicidal and plant growthregulating properties. Among those compounds which are to be singled outfor particular mention on account of their activity are the followinggroups:

Acylcyclohexanediones of formula I wherein

A is a 2- to 7-membered alkylene bridge,

n is 0, 1 or 2,

R₁ is C₁ -C₄ alkyl or benzyl,

R₂ is C₁ -C₆ alkyl which is unsubstituted or substituted by halogen, C₁-C₄ alkoxy or C₁ -C₄ alkylthio; or is C₃ -C₆ cycloalkyl; or phenyl,benzyl or phenylethyl, the phenyl ring of each of which may besubstituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio,C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, cyano or nitro, and

X is oxygen, preferably the compounds

5-(1-methylthiocyclobutan-1-yl)-2-(2,4-dichlorobenzoyl)cyclohexane-1,3-dione,

5-(1-methylthiocyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dione,

5-(1-methylthiocyclobutan-1-yl)-2-cyclopropylcarbonylcyclohexane-1,3-dione,

5-(1-methylthiocyclobutan-1-yl)-2-(2,3-dichlorobenzoyl)cyclohexane-1,3-dione,

5-(1-methylsulfonylcyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dione,

5-(1-methylthiocyclopropan-1-yl)-2-propionylcyclohexane-1,3-dione,

5-(1-ethylthiocyclopropan-1-yl)-2-propionylcyclohexane-1,3-dione and

5-(1-methylthiocyclopropan-1-yl)-2-n-butyrylcyclohexane-1,3-dione.

Oxime ethers of acylcyclohexanediones of formula I also to be singledout for particular mention are those wherein

A is a 2- to 7-membered alkylene bridge,

n is 0, 1 or 2,

R₁ is C₁ -C₄ alkyl or benzyl,

R₂ is C₁ -C₆ alkyl which is unsubstituted or substituted by halogen, C₁-C₄ alkoxy or C₁ -C₄ alkylthio,

X is the radical --NOR₃, and

R₃ is C₁ -C₆ alkyl, C₃ -C₆ haloalkyl, C₃ -C₆ alkenyl, C₃ -C₆ haloalkenylor C₃ -C₆ alkynyl, preferably the compounds

5-(1-methylthiocyclobutan-1-yl)-2-(1'-ethoximinobutyryl)cyclohexane-1,3-dione,

5-(1-methylthiocyclopropan-1-yl)-2-(1-ethoximinobutyryl)cyclohexane-1,3-dione,

5-(1-methylthiocyclohexan-1-yl)-2-(1-ethoximinobutyryl)cyclohexane-1,3-dione,

5-(1-methylthiocyclobutan-1-yl)-2-(1'-allyloxyiminobutyryl)cyclohexane-1,3-dione,

5-(1-methylthiocyclopentan-1-yl)-2-(1-ethoximinobutyryl)cyclohexane-1,3-dione,

5-(1-methylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloximino)-n-butyryl]cyclohexane-1,3-dione,

5-(1-methylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloximino)-propionyl]cyclohexane-1,3-dione,

5-(1-methylthiocyclopropan-1-yl)-2-[1-(cis-3-chloroallyloximino)propionyl]cyclohexane-1,3-dione,

5-(1-ethylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloximino)propionyl]cyclohexane-1,3-dioneand

5-(1-ethylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloximino)-n-butyryl]cyclohexane-1,3-dione.

These compounds may also be obtained in their tautomeric forms or assalts, in particular alkali metal and alkaline earth metal salts andalso manganese, copper, zinc and iron salts.

The salts correspond to the formula Ic ##STR3## wherein A, n, R₁, R₂ andR₃ have the meaning given under formula I and M⊕ is the ion-equivalentof a metal or a quaternary ammonium ion. Good activity showed

sodium-2-[1-(3-trans-chlorallyloxyamino)-propylidene]-3-oxo-5-(1-methylthio-1-cyclopropyl)-cyclohex-1-en-1-olate.

The acylcyclohexanediones and the oxime ethers thereof of the presentinvention are prepared in a manner known per se by reacting a1,3-cyclohexanedione which is suitably substituted in the 5-position bythe radical with an acid chloride or acid cyanide, and, if desired,further reacting the resultant 2-acyl-1,3-cyclohexanedione with ahydroxylamine. A first process for the preparation of theacylcyclohexanediones, and of the oxime ethers thereof, of formula Icomprises reacting a 1,3-cyclohexanedione derivative of formula II##STR4## wherein A, n and R₁ are as defined for formula I, with an acidhalide or acid anhydride of formula III ##STR5## wherein Y is a halogenatom or a radical ##STR6## and R₂ is as defined for formula I, in aninert organic solvent and in the presence of the equimolar amount of abase, and rearranging the resultant cyclohexanone ester of formula IV##STR7## wherein A, n, R₁ and R₂ are as defined for formula I, in aninert organic solvent and in the presence of a catalyst, to give the2-acyl-1,3-cyclohexanedione derivative of formula (Ia) ##STR8## whereinA, n, R₁ and R₂ are as defined for formula I, and, if desired, reactingsaid derivative of formula Ia with a hydroxylamine · hydrochloride offormula V

    H.sub.2 NOR.sub.3 ·HCl                            (V)

wherein R₃ is as defined for formula I, in an inert organic solvent andin the presence of the equimolar amount of a base, to give the oximeether of formula Ib ##STR9## wherein A, n, R₁, R₂ and R₃ are as definedfor formula I.

The rearrangement of the cyclohexanone ester of formula IV to give the2-acylcyclohexanedione derivative of formula Ia is effected e.g. bytreatment in an inert organic solvent and in the presence of a catalystor in an organic base as solvent. Examples of suitable catalysts arepyridine, 4-aminopyridine, 4-(dimethylamino)pyridine, aluminium(III)chloride in methylene chloride, collidine or lutidine, and alsocyanohydrines in the presence of a nitrogen base, such as e.g.triethylamine.

The cyclohexanone esters of formula IV are novel compounds. They and thepreparation thereof also constitute an object of the present invention.

A second more direct process for the preparation ofacylcyclohexanediones, and of the oxime ethers thereof, of formula Icomprises reacting a 1,3-cyclohexanedione derivative of formula II##STR10## wherein A, n and R₁ are as defined for formula I, with an acidcyanide of formula VI ##STR11## wherein R₂ is as defined for formula I,in an inert organic solvent or diluent and in the presence of zincchloride and a nitrogen base, and, if desired, reacting the resultant2-acyl-1,3-cyclohexanedione derivative of formula Ia ##STR12## whereinA, n, R₁ and R₂ are as defined for formula I, with a hydroxylamine ·hydrochloride of formula V

    H.sub.2 NOR.sub.3 ·HCl                            (V)

wherein R₃ is as defined for formula I, in an inert organic solvent andin the presence of the equimolar amount of a base, to give the oximeether of formula Ib ##STR13## wherein A, n, R₁, R₂ and R₃ are as definedfor formula I.

The salts of the acylhexanedione oxime ether of the formula Ic ##STR14##wherein A, n, R₁, R₂ and R₃ have the meaning given under formula I andM⊕ is the ion equivalent of a metal or a quaternary ammonium ion, byreacting a 2-acyl-1,3-cyclohexandione oxime ether of the formula Ib##STR15## wherein A, n, R₁, R₂ and R₃ have the above given meaning, inan inert solvent, with at least the equimolar amount of a hydroxide ofthe formula XVII

    M⊕--OH                                                 (XVII)

wherein M⊕ is the ion-equivalent of a metal or a quaternary ammonium ionand eliminating the water formed during the condensation, e.g. bydestillation.

Suitable organic solvents for these reactions are, in particular,aromatic compounds such as benzene or toluene, hydrohalogen compoundssuch as chloroform, dichloroethane or carbon tetrachloride, or esterssuch as ethyl acetate.

The reaction temperatures are in the range from room temperature to theboiling point of the reaction mixture. During the addition of acidchloride it may prove advisable to cool the reaction vessel.

Both inorganic and organic bases are suitable, e.g. pyridine,4-aminopyridine, 4-dimethylaminopyridine, collidine, triethylamine,ammonium carbonate, sodium carbonate, potassium carbonate or calciumcarbonate or the corresponding bicarbonates.

Such reactions are known. For the reaction with the acid halide or acidanhydride of formula III see Tetrahedron Letters 29 (1973) 249 orSynthesis 1978, 925; and for the reaction with the acid cyanide offormula V see published European patent application No. 90 262.

The starting cyclohexanediones of formula II are prepared in amultistage process.

An unsaturated methyl ketone of formula VII ##STR16## wherein A, n andR₁ are as defined for formula I, is reacted with a malonic acid diesterof formula VIII ##STR17## wherein R is a C₁ -C₆ alkyl radical or benzyl,in an absolute, inert organic solvent, in the presence of alkali metalmethylate and at the reflux temperature of the solvent, to give thecyclohex-1-en-2-ol-4-one ester of formula IX ##STR18## wherein A, n andR₁ are as defined for formula I, R is a C₁ -C₆ alkyl radical or benzyland Me⊕ is an alkali metal ion, saponifying said ester in the presenceof sodium hydroxide solution or potassium hydroxide solution, washingthe saponified ester with acid, then decarboxylating the resultant2,4-cyclohexanedione acid derivative of formula X ##STR19## wherein A, nand R₁ are as defined for formula I, in an inert solvent, and isolatingfrom the reaction mixture the cyclohexanedione of formula II required asstarting material ##STR20## wherein A, n and R₁ are as defined forformula I.

The reaction of the unsaturated methyl ketone of formula VII with themalonic acid diester of formula VIII is carried out in an absolutesolvent and in the presence of, preferably, sodium methylate orpotassium methylate. Preferred malonic acid esters are the ethyl andmethyl esters. The saponification and subsequent precipitation of theacid are effected in aqueous medium. The2,4-cyclohexanedione-1-carboxylic acid derivative of formula X is thenboiled in a solvent, e.g. water, toluene or xylene, or in achlorine-containing solvent, e.g. methylene chloride or chloroform,until the formation of carbonic acid ceases.

Another method of preparing the 1,3-cyclohexanedione derivatives offormula II comprises condensing an aldehyde of formula XI ##STR21##wherein A, n and R₁ are as defined for formula I, with malonic acid, ina basic solvent, to give the unsaturated acid of formula XII ##STR22##wherein A, n and R₁ are as defined for formula I. This acid is thenesterified in known manner with an alkanol R--OH, wherein R is C₁ -C₆alkyl or benzyl, and the resultant ester of formula XIV is thenring-closed with an acetoacetic acid alkyl ester of formula XV, in anabsolute solvent and in the presence of sodium methylate or potassiummethylate, in accordance with the following reaction scheme: ##STR23##

The condensation of the aldehyde of formula XI with malonic acid iscarried out either in a basic solvent such as pyridine, collidine orlutidine, or in an absolute alkanol, e.g. ethanol or methanol, in thepresence of sodium ethylate or sodium methylate.

The 1,3-cyclohexanedione derivatives of formula II are novel products.They and the preparation thereof constitute an object of the presentinvention.

The starting methyl ketones of formula VII are prepared by condensingaldehydes of formula XI with acetone and subsequently dehydrating theβ-hydroxyketone obtained as condensation product.

The reaction can be illustrated by the following scheme: ##STR24##

The condensation is effected in aqueous medium and in the presence of abase, e.g. sodium hydroxide solution or potassium hydroxide solution,advantageously at elevated temperature, e.g. at the boiling point of thereaction mixture.

The 1-alkylthiocycloalkylcarbaldehydes,1-alkylsulfinylcycloalkylcarbaldehydes and1-alkylsulfonylcycloalkylcarbaldehydes of formula IX are known; thepreparation thereof is described for example in GermanOffenlegungsschrift No. 2,120,908, or they can be prepared by aprocedure analogous to that disclosed in German Offenlegungsschrift No.2,403,236.

The unsaturated methyl ketones of formula VII are novel products. Theyand the preparation thereof constitute an object of the presentinvention.

The process for the preparation of the unsaturated methyl ketones offormula VII ##STR25## wherein A, n and R₁ are as described for formulaI, comprises condensing an aldehyde of formula XI ##STR26## wherein A, nand R₁ are as defined for formula I, with acetone, in basic aqueousmedium, then boiling the condensation product for several hours atreflux and subsequently isolating the resultant unsaturated methylketone from the reaction mixture.

A similar process for the preparation of unsaturated ketones isdescribed for example in Agr. Biol. Chem. 37 (1973), 261.

The described preparatory processes, including all partial steps,constitute an important object of the present invention. The novelcompounds are solids or oils whose use poses no problems.

The compounds of formula I have herbicidal and plant growth regulatingproperties and are suitable e.g. for selectively controlling grasses incrops of useful plants. The trans- and cis-3-chloroallyl oxime ethersare particularly active, especially the trans-isomers.

When used at low rates of application, the compounds of formula I havegood growth inhibiting and selective herbicidal properties which makethem preeminently suitable for use in crops of useful plants, inparticular in sugar beet, cereals, cotton, soybeans, maize and rice. Insome cases damage is also caused to weeds which have only beencontrolled up to now with total herbicides.

The compounds of formula I also have good plant growth regulatingproperties.

Surprisingly, it has now been found that the novel compounds of formulaI and compositions containing these compounds are characterised inparticular by their selective influence on plant metabolism. Thisselective influence on the physiological processes of plant developmentmakes it possible to use the compounds of formula I for differentpurposes, especially for those in connection with increasing the yieldof useful plants, with facilitating harvesting, and with labour-savingin measures taken in crops of cultivated plants.

Previous experience with plant growth regulators has shown that they areable to induce one or more different responses in the plants. Thesedifferent responses depend substantially on the time of application,based on the state of development of the seed or plant, as well as onthe concentrations of active substance applied to the plants or to thelocus thereof and on the nature of application. Growth regulators shouldat all events induce positive responses in the cultivated plants in thedesired manner.

Plant growth regulators may be used e.g. for inhibiting vegetative plantgrowth. Such a growth inhibition is of economic interest, inter alia, inrespect of grasses, as the frequency of cutting in flower gardens,parks, sports fields or road shoulders can thereby be reduced. Ofimportance too is the inhibition of growth of herbaceous and ligneousplants on road shoulders and near transmission lines, or generally inareas in which strong growth is undesirable.

The use of growth regulators for inhibiting the growth in height ofcereals is also important, as shortening the stalks diminishes orcompletely eliminates the danger of lodging before harvesting. Inaddition, growth regulators are able to bring about a strengthening ofthe stalks in crops of cereals, thereby also counteracting lodging.

Inhibition of the vegetative growth of many cultivated plants permitsmore plants to be sown in a crop area, so that a higher yield may beobtained per unit of area.

A further mechanism of yield increase using growth regulators resides inthe fact that nutrients are able increasingly to promote flowerformation and fruiting, whereas vegetative growth is inhibited.

Growth regulators are also frequently able to promote vegetative growth.This is very beneficial when the vegetative parts of plants are to beharvested. However, promotion of vegetative growth can also resultsimultaneously in promotion of generative growth, so that e.g. more orlarger fruit is formed.

Yield increases may also often be obtained by influencing the plantmetabolism without any visible changes in vegetative growth. Growthregulators can also induce a change in the composition of plants, sothat the quality of the harvest produce is improved. For example, it ispossible to increase the sugar content of sugar beet, sugar cane,pineapples and citrus fruit, or to increase the protein content ofsoybeans or cereals.

The use of growth regulators can lead to the formation of parthenocarpicfruit. The sex of blossoms can also be influenced.

The production or flow of secondary plant substances can also bepositively influenced by growth regulators, for example the stimulationof the flow of latex in rubber trees.

During plant growth, the development of side-shoots can also be promotedby the chemical interruption of apical dominance using growthregulators. This is of interest e.g. in the propagation of plantcuttings. However, it is also possible to inhibit the growth ofside-shoots, e.g. in tobacco plants after decapitation in order toprevent the formation of side-shoots, and thus to promote leaf growth.

With growth regulators it is also possible to speed up or delay theripening of harvest products before or after harvesting. This isparticularly advantageous, because a best possible accommodation tomarket requirements can thereby be achieved. In addition, growthregulators can often improve the colour of fruit. With the aid of growthregulators it is also possible to concentrate ripening at a particulartime. The conditions are thus created for a complete mechanicalharvesting of e.g. tobacco, tomatoes or coffee, or for manualharvesting, in only one single operation.

The application of growth regulators can also make it possible toinfluence the dormancy of seeds and buds of plants, i.e. the endogenicannual rhythm, so that plants, e.g. pineapples, or ornamentals innurseries, germinate, sprout or blossom at a time when they wouldnormally not tend to do so.

With growth regulators it is also possible to delay budding or thegermination of seeds, e.g. in order to avoid damage by late frosts inareas endangered thereby. Conversely, root growth and/or the formationof shoots can be stimulated, so that growth may be restricted to ashorter period.

Growth regulators can also impart halophilic properties to cultivatedplants. The conditions are thus created for cultivating plants in saltysoil.

Growth regulators can also induce resistance to frost and drought inplants.

Under the influence of growth regulators, the ageing (senescence) ofplants or parts of plants can be inhibited or delayed. Such an actioncan be of great economic importance, as the storability of treated partsof plants or whole plants such as fruit, berries, vegetables, salads orornamentals can be improved or prolonged after harvesting. Likewise, asubstantial yield increase can be obtained by treating cultivated plantsby prolonging the phase of photosynthetic activity.

A further important field of use for growth regulators is the inhibitionof excessive growth of tropical cover crops. In tropical and subtropicalmonocultures, e.g. in palm tree plantations, cotton and maize fieldsetc., cover crops, especially species of leguminosae, are often plantedtogether with the actual cultivated plants with the object ofmaintaining or improving the quality of the soil (prevention ofdesiccation, supplying nitrogen) and for preventing erosion. By applyingthe compounds of this invention it is possible to control the growth ofthese cover crops and so to keep the growth in height of these plants ata low level, thus ensuring healthy growth of the cultivated plants andthe maintenance of favourable soil conditions.

The compounds of formula I are normally applied in the form ofcompositions and can be applied to the crop area or plant to be treated,simultaneously or in succession, with further compounds. These furthercompounds can be both fertilisers or micronutrient donors or otherpreparations that influence plant growth. They can also be selectiveherbicides, insecticides, fungicides, bactericides, nematicides,molluscicides or mixtures of several of these preparations, if desiredtogether with further carriers, surfactants or application promotingadjuvants customarily employed in the art of formulation.

Suitable carriers and adjuvants can be solid or liquid and correspond tothe substances ordinarily employed in formulation technology, e.g.natural or regenerated mineral substances, solvents, dispersants,wetting agents, tackifiers, thickeners, binders or fertilisers.

A preferred method of applying a compound of formula I or anagrochemical composition containing at least one of said compounds, isfoliar application. The number of applications and the rate ofapplication depend on the manner in which growth is to be influenced.However, the compounds of formula I can also penetrate the plant throughthe roots via the soil (systemic action) by drenching the locus of theplant with a liquid composition, or by applying the compounds in solidform to the soil, e.g. in granular form (soil application). Thecompounds of formula I may also be applied to seeds (coating) by eitherimpregnating the seeds with a liquid formulation of the compound, orcoating them with a solid formulation. In special cases, further typesof application are also possible, e.g. selective treatment of the plantstems or buds.

The compounds of formula I are used in unmodified form or, preferably,together with the adjuvants conventionally employed in the art offormulation, and are therefore formulated in known manner toemulsifiable concentrates, coatable pastes, directly sprayable ordilutable solutions, dilute emulsions, wettable powders, solublepowders, dusts, granulates, and also encapsulations in e.g. polymersubstances. As with the nature of the compositions, the methods ofapplication, such as spraying, atomising, dusting, scattering orpouring, are chosen in accordance with the intended objectives and theprevailing circumstances. Advantageous rates of application are ingeneral from 10 g to 5 kg of active ingredient (a.i.) per hectare,preferably from 100 g to 3 kg a.i./ha, most preferably from 200 g to1000 g a.i./ha.

The formulations, i.e. the compositions, preparations or mixturescontaining the compound (active ingredient) of formula I and, whereappropriate, a solid or liquid adjuvant, are prepared in known manner,e.g. by intimately mixing and/or grinding the active components withextenders, e.g. with solvents, solid carriers, and optionallysurfaceactive compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycol,ethylene glycol monomethyl or monoethyl ether, ketones such ascyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone,dimethyl sulfoxide or dimethylformamide, as well as vegetable oils orepoxidised vegetable oils such as epoxidised coconut oil or soybean oil;or water.

The solid carriers used e.g. for dusts and dispersible powders arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorp-tivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable nonsorbent carriers are materials such ascalcite or sand. In addition, a great number of pregranulated materialsof inorganic or organic nature can be used, e.g. especially dolomite orpulverised plant residues.

Depending on the nature of the compound of formula I to be formulated,suitable surface-active compounds are non-ionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties.The term "surfactants" will also be understood as comprising mixtures ofsurfactants.

Suitable anionic surfactants can be both water-soluble soaps andwater-soluble synthetic surface-active compounds.

Suitable soaps are e.g. the alkali metal salts, alkaline earth metalsalts or unsubstituted or substituted ammonium salts of higher fattyacids (C₁₀ -C₂₂), e.g. the sodium or potassium salts of oleic or stearicacid, or of natural fatty acid mixtures which can be obtained e.g. fromcoconut oil or tallow oil. Mention may also be made of fatty acidmethyltaurin salts.

More frequently, however, so-called synthetic surfactants are used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metalsalts, alkaline earth metal salts or unsubstituted or substitutedammonium salts and contain a C₈ -C₂₂ alkyl radical which also includesthe alkyl moiety of acyl radicals, e.g. the sodium or calcium salt oflignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcoholsulfates obtained from natural fatty acids. These compounds alsocomprise the salts of sulfated and sulfonated fatty alcohol/ethyleneoxide adducts. The sulfonated benzimidazole derivatives preferablycontain 2 sulfonic acid groups and one fatty acid radical containing 8to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium,calcium or triethanolamine salts of dodecylbenzenesulfonic acid,dibutylnaphthalenesulfonic acid, or of a condensate ofnaphthalenesulfonic acid and formaldehyde. Also suitable arecorresponding phosphates, e.g. salts of the phosphoric acid ester of anadduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, or saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 30 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol, ethylenediamino-propyleneglycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms inthe alkyl chain, which adducts contain 20 to 250 ethylene glycol ethergroups and 10 to 100 propylene glycol ether groups. These compoundsusually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants arenonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylenesorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitablenon-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, benzylor hydroxy-lower alkyl radicals. The salts are preferably in the form ofhalides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammoniumchloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation aredescribed e.g. in the following publications:

"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp.,Ridgewood, N.J., 1979;

M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, ChemicalPublishing Co. Inc., N.Y., 1980-81;

H Stache, "Tensid Taschenbuch" (Handbook of Surfactants), 2nd edition,Carl Henser Verlag, Munich/Vienna 1981.

The formulations of this invention usually contain 0.1 to 99%,preferably 0.1 to 95%, of a compound of formula I, 1 to 99% of a solidor liquid adjuvant, and 0 to 25%, preferably 0.1 to 25%, of asurfactant.

Preferred formulations are composed in particular of the followingconstituents (%=percentage by weight):

    ______________________________________                                        Solutions                                                                     compound of formula I                                                                       5 to 95%, preferably                                                                              10  to 80%                                  solvent       95 to 5%, preferably                                                                              90  to 0%                                   surfactant    1 to 30%, preferably                                                                              2   to 20%                                  Emulsifiable                                                                  concentrates                                                                  compound of formula I                                                                       10 to 50%,                                                                              preferably                                                                              10  to 40%                                  surfactant    5 to 30%, preferably                                                                              10  to 20%                                  liquid carrier                                                                              20 to 95%,                                                                              preferably                                                                              40  to 80%                                  Dusts                                                                         compound of formula I                                                                       0.5 to 10%,                                                                             preferably                                                                              2   to 8%                                   solid carrier 99.5 to 90%,                                                                            preferably                                                                              98  to 92%                                  Suspension concentrates                                                       compound of formula I                                                                       5 to 75%, preferably                                                                              10  to 50%                                  water         94 to 25%,                                                                              preferably                                                                              90  to 30%                                  surfactant    1 to 40%, preferably                                                                              2   to 30%                                  Wettable powders                                                              compound of formula I                                                                       5 to 90%, preferably                                                                              10  to 80%                                                and most  preferably                                                                              20  to 60%                                  surfactant    0.5 to 20%                                                                              preferably                                                                              1   to 15%                                  solid carrier 5 to 90%, preferably                                                                              30  to 70%                                  Granulates                                                                    compound of formula I                                                                       0.5 to 30%                                                                              preferably                                                                              3   to 15%                                  solid carrier 99.5 to 70%,                                                                            preferably                                                                              97  to 85%.                                 ______________________________________                                    

Whereas commercial products will be preferably formulated asconcentrates, the end user will normally employ dilute formulations. Theformulations can be diluted to a concentration as low as 0.001% ofactive ingredient.

The compositions may also contain further ingredients such asstabilisers, antifoams, viscosity regulators, binders, tackifiers, aswell as fertilisers and other compounds for obtaining special effects.

Such agrochemical compositions constitute an object of the presentinvention.

The invention is illustrated by the following non-limitative Examples.

EXAMPLE 1 Preparation of1-(trans-but-3-en-2-on-4-yl)-1-methylthiocyclobutane (intermediate)##STR27##

With stirring, 140 ml of aqueous 2N sodium hydroxide solution are addeddropwise at 50° C. to a solution of 39 g ofcyclobutane-1-methylthio-1-carbaldehyde in 400 ml of acetone over 5minutes. The mixture is then stirred further for 15 minutes at roomtemperature and for 8 hours under reflux. Subsequently, the reactionmixture is concentrated, the residue is taken up in ether, the resultantethereal solution is washed with water and brine and dried, and theether is evaporated off. The residual oil is distilled at 0.013 mbar,affording 41.5 g of a clear oil with a boiling point of 58° C./0.013mbar and a content of title product of 96.5% (gas chromatography).

The intermediate methyl ketones of formula VII listed in Table 1 areprepared by procedures analogous to that of this Example.

                  TABLE 1                                                         ______________________________________                                         ##STR28##                   (VII)                                            Comp. R.sub.1   n     A     Physical data                                     ______________________________________                                        1.01  CH.sub.3  0     (CH.sub.2).sub.2                                                                    b.p. 54-55° C./0.13 mbar                   1.02  C.sub.2 H.sub.5                                                                         0     (CH.sub.2).sub.2                                                                    b.p. 66-69° C./0.13 mbar                   1.03  CH.sub.3  0     (CH.sub.2).sub.3                                                                    b.p. 58° C./0.13 mbar                      1.04  C.sub.2 H.sub.5                                                                         0     (CH.sub.2).sub.3                                                                    b.p. 70-72° C./0.05 mbar                   1.05  C.sub.3 H.sub.7 -n                                                                      0     (CH.sub.2).sub.3                                        1.06  CH.sub.3  0     (CH.sub.2).sub.4                                                                    b.p. 74° C./0.13 mbar                      1.07  C.sub.2 H.sub.5                                                                         0     (CH.sub.2).sub.4                                        1.08  benzyl    0     (CH.sub.3).sub.4                                        1.09  CH.sub.3  0     (CH.sub.2).sub.5                                                                    b.p. 85-88° C./0.013 mbar                  1.10  C.sub.2 H.sub.5                                                                         0     (CH.sub.2).sub.5                                                                    b.p. 90-92° C./0.013 mbar                  1.11  C.sub.3 H.sub.7 -n                                                                      0     (CH.sub.2).sub.5                                        1.12  CH.sub.3  0     (CH.sub.2).sub. 6                                       1.13  C.sub.2 H.sub.5                                                                         0     (CH.sub.2).sub.6                                        1.14  C.sub.3 H.sub.7 -n                                                                      0     (CH.sub.2).sub.2                                                                    b.p. 74-79° C./0.013 mbar                  1.15  CH(CH.sub.3).sub.2                                                                      0     (CH.sub.2).sub.2                                                                    b.p. 69-72° C./0.013 mbar                  1.16  benzyl    0     (CH.sub.2).sub.2                                                                    b.p. 138-141° C./0.013 mbar                1.17  CH.sub.3  1     (CH.sub.2).sub.2                                        1.18  CH.sub.3  2     (CH.sub.2).sub.2                                        1.19  CH.sub.3  1     (CH.sub.2).sub.3                                        1.20  CH.sub.3  2     (CH.sub.2).sub.3                                        ______________________________________                                    

EXAMPLE 2 Preparation of5-(1-methylthiocyclobutan-1-yl)cyclohexane-1,3-dione (intermediate)##STR29##

Over 15 minutes, 41 g of1-(trans-but-3-en-2-on-1-yl)-1-methylthiocyclobutane are added dropwiseto a stirred suspension of 33.5 g of dimethyl malonate and 47 g ofsodium methylate (30.8% in methanol) in 900 ml of absolute toluene. Thepasty reaction mixture is then heated over 5 hours to reflux, withmethanol being distilled off until a distillation temperature of 110° C.has been reached. The initially sparingly stirrable reaction mixturethereby turns to a fine suspension. After cooling, this suspension isevaporated to dryness, and the residue is washed with hexane, thusaffording 70 g of the sodium salt of5-(1-methylthiocyclobutan-1-yl)-6-methoxycarbonylcyclohex-1-en-3-on-1-olof the formula ##STR30## as intermediate.

This intermediate is dissolved in 250 ml of aqueous 2N potassiumhydroxide solution, and the resultant solution is stirred for 1 1/2hours at 80° C. The solution is then allowed to cool. When it reaches70° C., the slow dropwise addition of 80 ml of concentrated hydrochloricacid is commenced. After cooling, the product precipitates incrystalline form. The product is isolated by filtration and washed withwater until the washings are neutral. The product is then dried at40°-50° C. in a desiccator. Yield: 48 g. Melting point afterrecrystallisation from ethanol/water: 141°-143° C.

The intermediate 1,3-cyclohexanedione derivatives listed in Table 2 areprepared by procedures analogous to that of this Example:

                  TABLE 2                                                         ______________________________________                                         ##STR31##                   (II)                                             Comp.   R.sub.1   n       A     Physical data                                 ______________________________________                                        2.01    CH.sub.3  0       (CH.sub.2).sub.3                                                                    m.p.  141-143° C.                      2.02    C.sub.2 H.sub.5                                                                         0       (CH.sub.2).sub.3                                                                    m.p.  92.sub.]100° C.                  2.03    CH.sub.3  0       (CH.sub.2).sub.2                                                                    m.p.  140-145° C.                      2.04    C.sub.2 H.sub.5                                                                         0       (CH.sub.2).sub.2                                                                    m.p.  118-121° C.                      2.05    C.sub.3 H.sub.7 -n                                                                      0       (CH.sub.2).sub.2                                                                    m.p.  107-109° C.                      2.06    CH.sub.3  0       (CH.sub.2).sub.4                                                                    m.p.  138-140° C.                      2.07    C.sub.2 H.sub.5                                                                         0       (CH.sub.2).sub.4                                    2.08    C.sub.2 H.sub.5                                                                         1       (CH.sub.3).sub.4                                    2.09    C.sub.2 H.sub.5                                                                         2       (CH.sub.2).sub.4                                    2.10    CH.sub.3  0       (CH.sub.2).sub.5                                                                    m.p.  138-140° C.                      2.11    (C.sub.2 H.sub.5                                                                        0       (CH.sub.2).sub.5                                                                    m.p.  99-101° C.                       2.12    C.sub.3 H.sub.7 -n                                                                      0       (CH.sub.2).sub.5                                    2.13    benzyl    0       (CH.sub.2).sub.5                                    2.14    CH(CH.sub.3).sub.2                                                                      0       (CH.sub.2).sub.2                                                                    m.p.  98-104° C.                       2.15    benzyl    0       (CH.sub.2).sub.2                                                                    m.p.  163-165° C.                      2.16    CH.sub.3  1       (CH.sub.2).sub.2                                    2.17    CH.sub.3  2       (CH.sub.2).sub.2                                    2.18    C.sub.2 H.sub.5                                                                         1       (CH.sub.2).sub.2                                    2.19    C.sub.2 H.sub.5                                                                         2       (CH.sub.2).sub.2                                    2.20    CH.sub.3  1       (CH.sub.2).sub.3                                    2.21    CH.sub.3  2       (CH.sub.2).sub.3                                    ______________________________________                                    

EXAMPLE 3 Preparation of5-(1-methylthiocyclobutan-1-yl)-3-n-butyryloxycyclohex-2-en-1-one(intermediate) ##STR32##

A mixture of 13.8 g of cyclohexane-1,3-dione, 8.7 g of butyryl chlorideand 11.3 g of potassium carbonate in 250 ml of tetrahydrofuran isstirred for 4 hours at room temperature. The reaction mixture is thenconcentrated by evaporation and taken up in ether, and the resultantethereal solution is washed twice with water and once with brine anddried. The ether is evaporated off, and the residual oil ischromatographed through a flash column packed with silica gel [eluant: a1:2 mixture of ether and hexane]. The eluate is concentrated byevaporation, affording 10.2 g of a colourless oil; n_(D) ²⁶ =1.5275.

The intermediate cyclohexanone esters of formula IV listed in Table 3are prepared by procedures analogous to that of this Example.

                                      TABLE 3                                     __________________________________________________________________________     ##STR33##                                                                    Comp.                                                                              R.sub.1                                                                              n  A    R.sub.2 Physical data                                     __________________________________________________________________________    3.01 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    n.sub.D.sup.26 1.5275                             3.02 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   cyclopropyl                                                                           n.sub.D.sup.35 1.5478                             3.03 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    n.sub.D.sup.35 1.5218                             3.04 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.3                                                                   cyclopropyl                                               3.05 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       n.sub.D.sup.30 1.5253                             3.06 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    n.sub.D.sup.26 1.5210                             3.07 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   cyclopropyl                                                                           n.sub.D.sup.26 1.5413                             3.08 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    b.p. 142° C./0.013 mbar                    3.09 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   cyclopropyl                                                                           n.sub.D.sup.25 1.5358                             3.10 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       b.p. 137°/0.013 mbar                       3.11 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   CH(CH.sub.3).sub.2                                        3.12 CH.sub.3                                                                             0  (CH.sub.2).sub.4                                                                   C.sub.3 H.sub.7 -n                                                                    n.sub.D.sup.26 1.5297                             3.13 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.4                                                                   C.sub.3 H.sub.7 -n                                        3.14 CH.sub.3                                                                             0  (CH.sub.2).sub.4                                                                   cyclopropyl                                                                           n.sub.D.sup.26 1.5437                             3.15 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       n.sub.D.sup.26 1.5310                             3.16 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.4                                                                   C.sub.2 H.sub.5                                           3.17 CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   C.sub.3 H.sub.7 -n                                                                    n.sub.D.sup.30 1.5306                             3.18 CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   cyclopropyl                                                                           m.p. 90-91° C.                             3.19 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.5                                                                   C.sub.3 H.sub.7 -n                                                                    n.sub.D.sup.30 1.5263                             3.20 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.5                                                                   cyclopropyl                                               3.21 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   benzyl                                                    3.22 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       n.sub.D.sup.26 1.5356                             3.23 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.5                                                                   C.sub.2 H.sub.5                                                                       n.sub.D.sup.30 1.5333                             3.24 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.4                                                                   CH.sub.3                                                  3.25 CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   C.sub.2 H.sub.5                                                                       m.p. 76-77°  C.                            3.26 CH(CH.sub.3).sub.2                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       n.sub.D.sup.30 1.5167                             3.27 CH(CH.sub.3).sub.2                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    n.sub.D.sup.30 1.5125                             3.28 CH(CH.sub.3).sub.2                                                                   0  (CH.sub.2).sub.2                                                                   cyclopropyl                                                                           n.sub.D.sup.30 1.5298                             3.29 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       b.p. 140-142° C./0.013 mbar                3.30 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    b.p. 153-155° C./0.013 mbar                3.31 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   cyclopropyl                                                                           n.sub.D.sup.30 1.5290                             3.32 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   CH(CH.sub.3).sub.2                                                                    n.sub.D.sup.30 1.5096                             3.33 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   CH.sub.3                                                                              n.sub.D.sup.30 1.5303                             3.34 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.4 H.sub.9 -n                                        3.35 benzyl 0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       m.p. 69-71° C.                             3.36 benzyl 0  (CH.sub.2).sub.5                                                                   C.sub.3 H.sub.7 -n                                                                    n.sub.D.sup.30 1.5562                             3.37 CH.sub.3                                                                             1  (CH.sub.2).sub. 2                                                                  C.sub.2 H.sub.5                                           3.38 CH.sub.3                                                                             2  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                        3.39 CH.sub.3                                                                             2  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                           3.40 CH.sub.3                                                                             1  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                        3.41 CH.sub.3                                                                             1  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                           3.42 CH.sub.3                                                                             2  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                        3.43 benzyl 0  (CH.sub.2).sub.2                                                                   cyclopropyl                                                                           m.p. 62-64° C.                             __________________________________________________________________________

EXAMPLE 4 Preparation of5-(1-methylthiocyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dione##STR34##

A solution of 10.0 g of5-(1-methylthiocyclobutan-1-yl)-3-n-butyryloxycyclohex-2-en-1-one(Example 3) and 0.5 g of 4-(N,N-dimethylamino)pyridine is stirred for 3days at a temperature of 100°-110° C. The reaction mixture is thenconcentrated by evaporation. The residual oil is chromatographed througha colunm of 300 g of silica gel covered with a 1 cm thick layer ofaluminium oxide (acidic) [eluant: a 1:5 mixture of ether and hexane].The eluate is evaporated off, affording 8.1 g of title product in theform of a yellow oil; n_(D) ³⁵ =1.5498.

EXAMPLE 5 Preparation of5-(1-methylthiocyclobutan-1-yl)-2-(2,4-dichlorobenzoylcyclohexane-1,3-dion##STR35##

With cooling in an ice-bath and with stirring, 1.94 g of triethylamineare added dropwise to a mixture of 3.71 g of5-(1-methylthiocyclobutan-1-yl)cyclohexane-1,3-dione (Example 2), 3.85 gof 2,4-dichlorobenzoyl cyanide and 2.62 g of zinc chloride in 100 ml ofmethylene chloride. The reaction mixture is than allowed to warm to roomtemperature, and stirring is continued for 20 hours. The reactionmixture is then poured into a 1:1 mixture of ice and concentratedhydrochloric acid. After the addition of methylene chloride, the organicphase is spearated, washed twice with water, dried and concentrated byevaporation. The residue is chromatographed through a column of 150 g ofsilica gel covered with a 1 cm thick layer of aluminium oxide (Alox Iacidic) [eluant: a 1:1 mixture of ethyl acetate and hexane]. The eluateis concentrated by evaporation, and the residue is taken up in ether.Insoluble residue is filtered off. After the ether has been evaporatedoff, a viscous oil which congeals on standing is obtained. The oil istriturated in hexane, affording 3.4 g of crystalline material; m.p.:82°-83° C.

The 2-acyl-1,3-cyclohexanediones of formula Ia listed in Table 4 areprepared by procedures analogous to those of Examples 4 and 5.

                                      TABLE 4                                     __________________________________________________________________________     ##STR36##                          (Ia)                                      Comp.                                                                             R.sub.1                                                                             n  A   R.sub.2   Physical data                                      __________________________________________________________________________    4.01                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.3                                                                  C.sub.3 H.sub.7 -n                                                                      n.sub.D.sup.25 1.5498                              4.02                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.3                                                                  cyclopropyl                                                                             n.sub.D.sup.35 1.5753                              4.03                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.3                                                                  2,4-dichlorophenyl                                                                      m.p. 82-83° C.                              4.04                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.3                                                                  2,3-dichlorophenyl                                                                      m.p. 88-91° C.                              4.05                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.3                                                                  C.sub.3 H.sub.7 -n                                                                      n.sub.D.sup.30 1.5432                              4.06                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.3                                                                  cyclopropyl                                                  4.07                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.3                                                                  2,4-dichlorophenyl                                           4.08                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.3                                                                  4-chlorophenyl                                               4.09                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.4                                                                  C.sub.3 H.sub.7 -n                                                                      n.sub.D.sup.26 1.5536                              4.10                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.4                                                                  C.sub.3 H.sub.7 -n                                           4.11                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.4                                                                  cyclopropyl                                                  4.12                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.4                                                                  cyclopropyl                                                                             m.p. 80-82° C.                              4.13                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.4                                                                  2,4-dichlorophenyl                                           4.14                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.4                                                                  2,4-dichlorophenyl                                                                      m.p. 89-91° C.                              4.15                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.4                                                                  C.sub.2 H.sub.5                                              4.16                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.4                                                                  CH(CH.sub.3).sub.2                                           4.17                                                                              C.sub.2 H.sub.5                                                                     2  (CH.sub.2).sub.4                                                                  C.sub.3 H.sub.7 -n                                           4.18                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.5                                                                  C.sub.3 H.sub.7 -n                                                                      n.sub.D.sup.30 1.5541                              4.19                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.5                                                                  C.sub.3 H.sub.7 -n                                                                      n.sub.D.sup.30 1.5483                              4.20                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.5                                                                  cyclopropyl                                                  4.21                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.5                                                                  cyclopropyl                                                                             n.sub.D.sup.30 1.5711                              4.22                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.5                                                                  2,4-dichlorophenyl                                           4.23                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.5                                                                  2-chlorophenyl                                               4.24                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.5                                                                  C.sub.2 H.sub.5                                                                         m.p. 100-101° C.                            4.25                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.3                                                                  C.sub.2 H.sub.5                                                                         n.sub.D.sup.26 1.5566                              4.26                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.4                                                                  4-chlorophenyl                                                                          m.p. 108-110° C.                            4.27                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.2                                                                  cyclopropyl                                                                             m.p. 71-73° C.                              4.28                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.2                                                                  C.sub.3 H.sub.7 -n                                                                      m.p. 61-62° C.                              4.29                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                                                         m.p. 74-76° C.                              4.30                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.2                                                                  cyclopropyl                                                                             n.sub.D.sup.30 1.5653                              4.31                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.2                                                                  C.sub.3 H.sub.7 -n                                                                      m.p. 60-61° C.                              4.32                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                                                         m.p. 50-51° C.                              4.33                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.2                                                                  2,4-dichlorophenyl                                                                      m.p. 80-82° C.                              4.34                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.5                                                                  C.sub.2 H.sub.5                                                                         m.p. 69-71° C.                              4.35                                                                              CH.sub. 3                                                                           0  (CH.sub.2).sub.5                                                                  2,4-dichlorophenyl                                                                      m.p. 103-106° C.                            4.36                                                                              C.sub.2 H.sub.5                                                                     0  (CH.sub.2).sub.3                                                                  C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 1.5487                              4.37                                                                              CH(CH.sub.3).sub.2                                                                  0  (CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 1.5398                              4.38                                                                              CH(CH.sub.3).sub.2                                                                  0  (CH.sub.2).sub.2                                                                  C.sub.3 H.sub.7 -n                                                                      n.sub.D.sup.30 1.5338                              4.39                                                                              CH(CH.sub.3).sub.2                                                                  0  (CH.sub.2).sub.2                                                                  cyclopropyl                                                                             n.sub.D.sup.30 1.5590                              4.40                                                                              C.sub.3 H.sub.7 -n                                                                  0  (CH.sub.2).sub.2                                                                  cyclopropyl                                                                             n.sub.D.sup.30 1.5574                              4.41                                                                              C.sub.3 H.sub.7 -n                                                                  0  (CH.sub.2).sub.2                                                                  CH(CH.sub.3).sub.2                                                                      n.sub.D.sup.30 1.5339                              4.42                                                                              C.sub.3 H.sub.7 -n                                                                  0  (CH.sub.2).sub.2                                                                  C.sub.3 H.sub.7 -n                                                                      b.p. 153-155°/0.013 mbar                    4.43                                                                              C.sub.3 H.sub.7 -n                                                                  0  (CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                                                         b.p. 150-152°/0.013 mbar                    4.44                                                                              benzyl                                                                              0  (CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 1.5834                              4.45                                                                              benzyl                                                                              0  (CH.sub.2).sub.2                                                                  cyclopropyl                                                                             m.p. 112-113° C.                            4.46                                                                              benzyl                                                                              0  (CH.sub.2).sub.2                                                                  C.sub.3 H.sub.7 -n                                                                      n.sub.D.sup.30 1.5752                              4.47                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.2                                                                  C.sub.4 H.sub.9 -n                                           4.48                                                                              CH.sub.3                                                                            0  (CH.sub.2).sub.2                                                                  CH.sub.3  m.p. 80-82° C.                              4.49                                                                              CH.sub.3                                                                            1  (CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                              4.50                                                                              CH.sub.3                                                                            1  (CH.sub.2).sub.2                                                                  C.sub.3 H.sub.7 -n                                           4.51                                                                              CH.sub.3                                                                            2  (CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                              4.52                                                                              CH.sub.3                                                                            2  (CH.sub.2).sub.2                                                                  C.sub.3 H.sub.7 -n                                           4.53                                                                              CH.sub.3                                                                            1  (CH.sub.2).sub.3                                                                  C.sub.2 H.sub.5                                              4.54                                                                              CH.sub.3                                                                            2  (CH.sub.2).sub.3                                                                  C.sub.2 H.sub.5                                              4.55                                                                              CH.sub.3                                                                            1  (CH.sub.2).sub.3                                                                  C.sub.3 H.sub.7 -n                                           4.56                                                                              CH.sub.3                                                                            2  (CH.sub.2).sub.3                                                                  C.sub.3 H.sub.7 -n                                           __________________________________________________________________________

EXAMPLE 6 Preparation of5-(1-methylthiocyclobutan-1-yl)-2-(3-oxa-4-azaoct-4-en-5-yl)cyclohexane-1,3-dione[5-(1-methylthiocyclobutan-1-yl)-2-(1-ethoximinobutyryl)cyclohexane-1,3-dione]##STR37##

A mixture of 3.0 g of5-(1-methylthiocyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dione(Example 4), 1.15 g of O-ethylhydroxylamine·hydrochloride and 1.5 g ofpotassium carbonate in 30 ml of chloroform and 3 ml of methanol isstirred for 3 days at room temperature. The reaction mixture is thenevaporated to dryness, the residue is taken up in ether, and theethereal layer is washed first with water and then with 1N hydrochloricacid. The ethereal layer is extracted cold with 2N potassium hydroxidesolution, and the aqueous layer is rewashed with ether. Thebasic-aqueous extract is made cold and then neutralised with ice-coldsemi-concentrated hydrochloric acid to pH 5.5. Subsequently, the batchis again extracted with ether, the ethereal layer is dried over sodiumsulfate and filtered, the filtrate is concentrated by evaporation, andthe residue is taken up in pentane. The pentane solution is treated withactive carbon and filtered, and the filtrate is concentrated byevaporation, thus affording 2.5 g of title product in the form of acolourless oil; n_(D) ³⁰ =1.5428.

The oxime ethers of 2-acyl-1,3-cyclohexandiones of formula Ib listed inTable 5 are prepared by procedures analogous to that of Example 6.

                                      TABLE 5                                     __________________________________________________________________________     ##STR38##                                    (Ib)                            Comp.                                                                              R.sub.1                                                                              n  A    R.sub.2 R.sub.3     Physical data                         __________________________________________________________________________    5.01 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5428                 5.02 CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5429                 5.03 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCH.sub.2                                                                       n.sub.D.sup.30 1.5468                 5.04 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           n.sub.D.sup.31 1.5541                 5.05 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5356                 5.06 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5410                 5.07 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.4 H.sub.9 -n                                5.08 C.sub.2 H.sub.5                                                                      2  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                   5.09 CH.sub.3                                                                             2  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                   5.10 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCH.sub.2                                                                       n.sub.D.sup.30 1.5360                 5.11 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5312                 5.12 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           n.sub.D.sup.30 1.5460                 5.13 CH.sub.3                                                                             0  (CH.sub.2).sub.4                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5426                 5.14 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.4                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                   5.15 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.4                                                                   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                   5.16 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.4                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.3                                          5.17 C.sub.2 H.sub.5                                                                      2  (CH.sub.2).sub.4                                                                   C.sub.2 H.sub.5                                                                       C.sub.4 H.sub.9 -n                                5.18 C.sub.2 H.sub.5                                                                      1  (CH.sub.2).sub.4                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                   5.19 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.5                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5398                 5.20 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.5                                                                   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5450                 5.21 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.5                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCH.sub.2                                                                       n.sub.D.sup.30 1.5449                 5.22 CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           n.sub.D.sup.30 1.5571                 5.23 CH.sub.3                                                                             0  (CH.sub.2).sub.4                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           n.sub.D.sup.30 1.5569                 5.24 CH.sub.3                                                                             0  (CH.sub.2).sub.4                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCH.sub.2                                                                       n.sub.D.sup.30 1.5480                 5.25 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.4 H.sub.9 -n                                                                        n.sub.D.sup.30 1.5324                 5.26 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       C.sub.4 H.sub.9 -n                                                                        n.sub.D.sup.30 1.5383                 5.27 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5362                 5.28 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCH.sub.2                                                                       n.sub.D.sup.30 1.5420                 5.29 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           n.sub.D.sup.30 1.5514                 5.30 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5302                 5.31 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           m.p. 65-69° C.                 5.32 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5359                 5.33 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       C.sub.4 H.sub.9 -n                                                                        n.sub.D.sup.30 1.5288                 5.34 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           n.sub.D.sup.30 1.5558                 5.35 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           n.sub.D.sup.30 1.5496                 5.36 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       CH.sub.3    n.sub.D.sup.30 1.5539                 5.37 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5469                 5.38 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           n.sub.D.sup.30 1.5613                 5.39 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           n.sub.D.sup.30 1.5568                 5.40 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.4 H.sub.9 -n                                                                        n.sub.D.sup.30 1.5242                 5.41 C.sub.2 H.sub.5                                                                      0  (CH.sub.3).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCH.sub.2                                                                       n.sub.D.sup.30 1.5407                 5.42 C.sub.2 H.sub.5                                                                      0  (CH.sub.3).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           n.sub.D.sup.30 1.5514                 5.43 CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.4 H.sub.9 -n                                                                        n.sub.D.sup.30 1.5379                 5.44 CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5496                 5.45 CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCH.sub.2                                                                       n.sub.D.sup.30 1.5547                 5.46 CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           n.sub.D.sup.30 1.5631                 5.47 CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   C.sub.2 H.sub.5                                                                       C.sub.4 H.sub.9 -n                                                                        n.sub.D.sup.30 1.5415                 5.48 CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   C.sub.2 H.sub.5                                                                       CH.sub.3    n.sub.D.sup.30 1.5565                 5.49 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.5                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           n.sub.D.sup.30 1.5526                 5.50 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5578         5.51 CH.sub.3                                                                             0  (CH.sub.3).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           (cis) n.sub.D.sup. 30 1.5570          5.52 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5519         5.53 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5464         5.54 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           (cis) n.sub.D.sup.30 1.5511           5.55 C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           (cis) n.sub.D.sup.30 1.5460           5.56 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.3    n.sub.D.sup.30 1.5491                 5.57 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCH.sub.2                                                                       m.p. 46-49° C.                 5.58 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5516         5.59 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           (cis) n.sub.D.sup.30 1.5510           5.60 CH(CH.sub.3).sub.2                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5315                 5.61 CH(CH.sub.3).sub.2                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCH.sub.2                                                                       n.sub.D.sup.30 1.5372                 5.62 CH(CH.sub.3).sub.2                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5469         5.63 CH(CH.sub.3).sub.2                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5258                 5.64 CH(CH.sub.3).sub.2                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCH.sub.2                                                                       n.sub.D.sup.30 1.5322                 5.65 CH(CH.sub.3).sub.2                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5431         5.66 CH(CH.sub.3).sub.2                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.3    n.sub.D.sup.30 1.5313                 5.67 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CClCH.sub.2                                                                      n.sub.D.sup.30 1.5538                 5.68 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5472         5.69 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CClCH.sub.2                                                                      n.sub.D.sup.30 1.5440                 5.70 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCH.sub.2                                                                       n.sub.D.sup.30 1.5370                 5.71 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5268                 5.72 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5420         5.73 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CClCH.sub.2                                                                      n.sub.D.sup.30 1.5390                 5.74 C.sub.3 H.sub.7 -n                                                                   0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.4 H.sub.9 -n                                                                        n.sub.D.sup.30 1.5208                 5.75 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CBrCH.sub.2                              5.76 benzyl 0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           m.p. 115-117° C.               5.77 benzyl 0  (CH.sub.2).sub.2                                                                   C.sub. 2 H.sub.5                                                                      CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5792         5.78 benzyl 0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5478                 5.79 benzyl 0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5706         5.80 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.7 -n                                5.81 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       C.sub.4 H.sub.9 -n                                                                        n.sub.D.sup.30 1.5323                 5.82 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CCH                                                                              n.sub.D.sup.30 1.5533                 5.83 CH.sub.3                                                                             1  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5640         5.84 CH.sub.3                                                                             2  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.40 1.5500         5.85 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CClCH.sub.2                                                                      n.sub.D.sup.30 1.5487                 5.86 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.3 H.sub.7 -n                                5.87 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CCH                                                                              n.sub.D.sup.30 1.5476                 5.88 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   CH.sub.3                                                                              CH.sub.3                                          5.89 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHBr                                                                           (trans)                               5.90 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHBr                                                                           n.sub.D.sup.30 1.5679                 5.91 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   CH.sub.3                                                                              C.sub.2 H.sub.5                                                                           n.sub.D.sup.30 1.5469                 5.92 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHBr                                                                           (trans)                               5.93 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHBr                                                                           n.sub.D.sup.30 1.5619                 5.94 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   CH.sub.3                                                                              CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.30 1.5637         5.95 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.25 1.5618         5.96 CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           (trans) n.sub.D.sup.25 1.5568         5.97 CH.sub.3                                                                             1  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                   5.98 CH.sub.3                                                                             2  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                   5.99 CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.4 H.sub.9 -n                                                                    CH.sub.2 CHCHCl                                                                           (trans)                               5.100                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.4 H.sub.9 -n                                                                    C.sub.2 H.sub.5                                   5.101                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCCl.sub.2                                                                      n.sub.D.sup.30 1.5609                 5.102                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCCl.sub.2                              5.103                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCCl.sub.2                              5.104                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCCl.sub.2                              5.105                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CClCClH                                  5.106                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CClCHCl                                  5.107                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CClCHCl                                  5.108                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CClCHCl                                  5.109                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCH.sub.3                                                                     (trans) n.sub.D.sup.30 1.5450         5.110                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCH.sub.3                                                                     (trans)                               5.111                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCH.sub.3                                                                     (trans) n.sub.D.sup.30 1.5401         5.112                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCH.sub.3                                                                     (trans)                               5.113                                                                              CH.sub.3                                                                             0  (CH.sub.3).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCClCH.sub.3                                                                    n.sub.D.sup.30 1.5543                 5.114                                                                              CH.sub.3                                                                             0  (CH.sub.3).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCClCH.sub.3                            5.115                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.3).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCClCH.sub.3                                                                    (trans)                               5.116                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.3).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCClCH.sub.3                            5.117                                                                              CH.sub. 3                                                                            0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCClCH.sub.3                                                                    (trans)                               5.118                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCClCH.sub.3                            5.119                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCClCH.sub.3                                                                    (trans)                               5.120                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCClCH.sub.3                            5.121                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHClCHCH.sub.2                           5.122                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHClCHCH.sub.2                           5.123                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHClCHCH.sub.2                           5.124                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHClCHCH.sub.2                           5.125                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCHCH.sub.2 Cl                          5.126                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCH.sub.2 Cl                          5.127                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub. 2 CH.sub.2 CH.sub.2 Cl                    5.128                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CH.sub.2 CH.sub.2 Cl                     5.129                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CH.sub.2 Cl                              5.130                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CH(CH.sub.3).sub.2                       5.131                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CH(CH.sub.3).sub.2                       5.132                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   CH.sub.2 OCH.sub.3                                                                    CH.sub.2 CHCHCl                                                                           (trans)                               5.133                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   benzyl  CH.sub.2 CHCHCl                                                                           (trans)                               5.134                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   phenyl-ethyl                                                                          CH.sub.2 CHCHCl                                                                           (trans)                               5.135                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 F.sub.5                                                                       C.sub.2 H.sub.5                                   5.136                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 F.sub.5                                                                       CH.sub.2 CHCHCl                                                                           (trans)                               5.137                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CHCHCl                                                                           (trans)                               5.138                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.2 H.sub.5                                   5.139                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub. 2                                                                  CF.sub.3                                                                              C.sub.2 H.sub.5                                   5.140                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CClCClCH.sub.3                                                                   (trans)                               5.141                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CClCClCH.sub.3                                                                   (trans)                               5.142                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CClCClCH.sub.3                                                                   (cis)                                 5.143                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2 CClCClCH.sub.3                                                                   (cis)                                 5.144                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.5                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2CHCH.sub.2                                                                        n.sub.D.sup.30 1.5491                 5.145                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   CH.sub.3                                                                              CH.sub.2CClCH.sub.2                                                                       n.sub.D.sup.30 1.5592                 5.146                                                                              benzyl 0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       C.sub.4 H.sub.9 -n                                                                        m.p. 57-59° C.                 5.147                                                                              benzyl 0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHCH.sub.2                                                                       m.p. 85-87° C.                 5.148                                                                              benzyl 0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    C.sub.4 H.sub.9 -n                                                                        n.sub.D.sup.30 1.5472                 5.149                                                                              benzyl 0  (CH.sub.2).sub.2                                                                   C.sub.3 H.sub.7 -n                                                                    CH.sub.2CHCH.sub.2                                                                        n.sub.D.sup.30 1.5490                 5.150                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2CCCH.sub.3                                5.151                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2CHCHBr                                    5.152                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2CCH                                       5.153                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CClCH.sub.2                              5.154                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2CHCHCH.sub.3                                                                      (trans)                               5.155                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 (n)                                                                   CH.sub.2CHCHBr                                    5.156                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 (n)                                                                   CH.sub.2CCH                                       5.157                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 (n)                                                                   CH.sub.2CClCH.sub.2                               5.158                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 (n)                                                                   CH.sub.2CHCHCH.sub.3                                                                      (trans)                               5.159                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 (n)                                                                   CH.sub.2CHCHCl                                                                            (trans) n.sub.D.sup.30 1.5505         5.160                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2CHCHCl                                                                            n.sub.D.sup.25 1.5614                 5.161                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.3                                                                   C.sub.3 H.sub.7 (n)                                                                   CH.sub.2CHCHCl                                                                            (cis) n.sub.D.sup.25 1.5564           5.162                                                                              C.sub.2 H.sub.5                                                                      0  (CH.sub.2).sub.3                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2CHCHCl                                                                            (trans) n.sub.D.sup.25 1.5580         5.163                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2 CHC(CH.sub.3).sub.2                                                              n.sub.D.sup.30 1.5460                 5.164                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2CFCHCH.sub.3                                                                      (trans) n.sub.D.sup.30 1.5381         5.165                                                                              CH.sub.3                                                                             0  (CH.sub.2).sub.2                                                                   C.sub.2 H.sub.5                                                                       CH.sub.2CClCCl.sub.2                                                                      n.sub.D.sup.30 1.5619                 __________________________________________________________________________

EXAMPLE 7 Sodium2-[1-(3-trans-chloroallyloxyamino)propylidene]-3-oxo-5-(1-methylthio-1-cyclopropyl)-cyclohex-1-en-1-olate##STR39##

A solution of 0.015 g (0.04 Mol) sodium hydroxide in 3 ml of water areadded, while stirring vigorously to a solution of 5.16 g (0.015 Mol)2-[1-(3-trans-chloroallyloxyamino)-propyliden]-5-(1-methylthio-1-cyclohexan-1,3-dionin 10 ml of tetrahydrofuran. Stirring is continued for 5 minutes and thesolution is then evaporated to dryness in a rotatory evaporator at 50°C. The residue is dryed under high vacuum during 6 hours. The sodiumsalt is obtained in the form of a dry foam which still contains 1/4molecule of tetrahydrofuran. The salts listed in Table 6 are prepared inaccordance with the method of Example 7.

                                      TABLE 6                                     __________________________________________________________________________     ##STR40##                                                                    No.                                                                              R.sub.1                                                                          n A   R.sub.2     R.sub.3                                                                            M        phys. Daten                             __________________________________________________________________________    6.01                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    Na.sup.⊕                                                                           solid foam                              6.02                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    K.sup.⊕                                      6.03                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    Li.sup.⊕                                                                           solid foam                              6.04                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    1/2 Ca.sup.2.sup.⊕                           6.05                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    NH.sub.4                                         6.06                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    NH.sub.3 CH.sub.3                                6.07                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    NH.sub.2 (CH.sub.3).sub.2                        6.08                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    NH.sub.2 (C.sub.2 H.sub.5).sub.2                 6.09                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    NH.sub.3 C.sub.2 H.sub.5                         6.10                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    NH.sub.2 (C.sub.3 H.sub.7 iso).sub.2             6.11                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    N(CH.sub.3).sub.3 C.sub.2 H.sub.4 OH             6.12                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.3                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    Li.sup.⊕                                     6.13                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                    Li.sup.⊕                                     6.14                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    1/2  Cu.sup.2⊕                               6.15                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    1/2 Mg.sup.2⊕                                6.16                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    1/2 Zn.sup.2⊕                                6.17                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    NH.sub.3 C.sub.3 H.sub.7 iso                     6.18                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    NH.sub.3 C.sub.3 H.sub.7 -n                      6.19                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.3 H.sub.7 -n                                                                 Na.sup.⊕                                     6.20                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                                                           C.sub.3 H.sub.7 -n                                                                 Na.sup.⊕                                     6.21                                                                             C.sub.2 H.sub.5                                                                  0 (CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                    Na.sup.⊕                                     6.22                                                                             C.sub.2 H.sub.5                                                                  0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    Na.sup.⊕                                     6.23                                                                             C.sub.2 H.sub.5                                                                  0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.3 H.sub.7 -n                                                                 Na.sup.⊕                                     6.24                                                                             C.sub.2 H.sub.5                                                                  0 (CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                                                           C.sub.3 H.sub.7 -n                                                                 Na.sup.⊕                                     6.25                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    1/2 Ba.sup.2⊕                                6.26                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCl trans                                                                     C.sub.2 H.sub.5                                                                    N(CH.sub.3).sub.3 benzyl                         6.27                                                                             CH.sub.3                                                                         0 (CH.sub.2).sub.2                                                                  CH.sub.2 CHCHCH.sub.3 trans                                                               C.sub.2 H.sub.5                                                                    Na.sup.⊕                                     __________________________________________________________________________

EXAMPLE 8 Formulation Examples for compounds of formula I (percentagesare by weight)

    ______________________________________                                        (a) Wettable powders (a)    (b)      (c)                                      ______________________________________                                        compound of Table 4 or 5                                                                           20%    60%      0.5%                                     sodium lignosulfonate                                                                               5%     5%       5%                                      sodium laurylsulfate  3%    --       --                                       sodium diisobutylnaphthalenesulfonate                                                              --      6%       6%                                      octylphenol polyethylene glycol ether                                                              --      2%       2%                                      (7-8 moles of ethylene oxide)                                                 highly dispersed silicic acid                                                                       5%    27%      27%                                      kaolin               67%    --       --                                       sodium chloride      --     --       59.5%                                    ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants, and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        (b) Emulsifiable concentrates                                                                        (a)    (b)                                             ______________________________________                                        compound of Table 4 or 5                                                                             10%     1%                                             octylphenol polyethylene glycol ether                                                                 3%     3%                                             (4-5 moles of ethylene oxide)                                                 calcium dodecylbenzenesulfonate                                                                       3%     3%                                             castor oil polyglycol ether                                                                           4%     4%                                             (36 moles of ethylene oxide)                                                  cyclohexanone          30%    10%                                             xylene mixture         50%    79%                                             ______________________________________                                    

Emulsions of any required concentration can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        (c) Dusts           (a)     (b)                                               ______________________________________                                        compound of Table 4 or 5                                                                           0.1%    1%                                               talcum              99.9%   --                                                kaolin              --      99%                                               ______________________________________                                    

Dusts which are ready for use are obtained by mixing the activeingredient with the carrier, and grinding the mixture in a suitablemill.

    ______________________________________                                        (d) Extruder granulates                                                                            (a)    (b)                                               ______________________________________                                        compound of Table 4 or 5                                                                           10%     1%                                               sodium lignosulfonate                                                                               2%     2%                                               carboxymethylcellulose                                                                              1%     1%                                               kaolin               87%    96%                                               ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is subsequently moistened with water. The mixture is extrudedand then dried in a stream of air.

    ______________________________________                                        (e) Coated granulate                                                          ______________________________________                                        compound of Table 4 or 5                                                                              3%                                                    polyethylene glycol (mol. wt. 200)                                                                    2%                                                    kaolin                 94%                                                    ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coatedgranulates are obtained in this manner.

    ______________________________________                                        (f) Suspension concentrates                                                                           (a)    (b)                                            ______________________________________                                        compound of Table 4 or 5                                                                              40%     5%                                            ethylene glycol         10%    10%                                            nonylphenol polyethylene glycol ether                                                                  6%     1%                                            (15 moles of ethylene oxide)                                                  sodium lignosulfonate   10%     5%                                            carboxymethylcellulose   1%     1%                                            37% aqueous formaldehyde solution                                                                     0.2%   0.2%                                           silicone oil in the form of a 75%                                                                     0.8%   0.8%                                           aqueous emulsion                                                              water                   32%    77%                                            ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

    ______________________________________                                        (g) Salt solution                                                             ______________________________________                                        compound of Table 4 or 5                                                                               5%                                                   isopropylamine           1%                                                   octylphenol polyethylene glycol ether                                                                  3%                                                   (78 moles of ethylene oxide)                                                  water                   91%                                                   ______________________________________                                    

EXAMPLE 9 Preemergence herbicidal action

In a greenhouse, plant seeds are sown in flower pots of 11 cm diameter.Immediately after sowing, the surface of the soil is treated with anaqueous emulsion of the test compounds. A concentration of 4 kg of testcompound per hectare is applied. The pots are then kept in thegreenhouse at 22°-25° C. and 50-70% relative humidity. 3 weeks later thetest is evaluated and the action on the test plants is assessed. In thistest, compounds of Tables 4 and 5 exhibit good activity, in particularagainst the monocotyledenous test plants.

EXAMPLE 10 Postemergence herbicidal action

In a greehouse, various cultivated plants and weeds are reared fromseeds, in pots, until they have reached the 4- to 6-leaf stage. Theplants are then sprayed with aqueous emulsions of the test compounds(obtained from a 25% emulsifiable concentrate) at a rate of applicationof 4 kg/ha. The treated plants are then kept at optimum conditions oflight, regular watering, temperature (22°-25° C. ) and relative humidity(50-70%). The test is evaluated 15 days after treatment. The state ofthe plants is assessed according to the following scale

9 plant grows normally, like untreated control

7-8 slight phytotoxic symptoms

6 phytotoxic symptoms, the plant can recover

5 plant stunted

4 phytotoxic damage

2-3 severe damage

1 plant withered.

In this test compound 5.50 has been compared with 3 known compounds:

A5-(2-ethylthioprop-1-yl)-2[1-(ethoximino)butyryl]-cyclohexane-1,3-dione,known from U.S. Pat. No. 4,249,937, Example 15-(2-ethylthioprop-1-yl)-2[1-(trans-3-chloroallyloximino)butyryl]-cyclohexane-1,3-dione,known from U.S. Pat. No. 4,440,556, compound 54

C5-(2-ethylthioprop-1-yl)-2-[1-(trans-3-chloroallyloximino)propionyl]-cyclohexane-1,3-dione,known from German Pat. No. 3,627,410, Example 3.

    ______________________________________                                        Compound tested         5.50     A   B     C                                  ______________________________________                                        plant       application rate                                                  Avena fatua 250 g/ha    1        2   1     1                                              125 g/ha    1        9   1     2                                               60 g/ha    1        9   6     9                                               30 g/ha    1        9   8     9                                  Bromus      250 g/ha    1        3   3     1                                  tectorum    125 g/ha    2        8   4     2                                               60 g/ha    2        9   7     3                                               30 g/ha    5        9   9     9                                  Lolium perenne                                                                            250 g/ha    1        1   1     2                                              125 g/ha    1        3   1     3                                               60 g/ha    1        4   4     7                                               30 g/ha    1        7   7     8                                  Alopecurus  250 g/ha    1        2   1     2                                  myosuroides 125 g/ha    1        3   2     2                                               60 g/ha    2        9   4     3                                               30 g/ha    2        9   6     4                                  Digitaria   250 g/ha    1        3   1     1                                  sanguinalis 125 g/ha    1        4   3     3                                               60 g/ha    2        6   8     5                                               30 g/ha    3        9   9     8                                  Echinochloa 250 g/ha    1        1   1     1                                   crus galli 125 g/ha    1        4   4     1                                               60 g/ha    1        6   6     4                                               30 g/ha    3        9   8     7                                  Sorghum     250 g/ha    1        2   3     1                                  halepense   125 g/ha    1        5   5     1                                               60 g/ha    2        7   7     4                                               30 g/ha    4        9   9     7                                  ______________________________________                                    

In this test, the compound 5.50 is herbicidally active at 30 g/ha,concentration at which the phytotoxic activity of the other compounds islow or inexistant.

EXAMPLE 11 Growth inhibition of tropical leguminous cover crops

The test plants (Centrosema plumieri and Centrosema pubescens) arereared until fully grown and then cut back to a height of 60 cm. Theplants are sprayed 7 days later with an aqueous emulsion of the testcompound. The test plants are kept at 70% relative humidity and 6000 luxartifical light for 14 hours per day, at day temperatures of 27° C. andnight temperatures of 21° C. The test is evaluated 4 weeks afterapplication by assessing and weighing the new growth compared withcontrols and by determining the phytotoxicity.

In this test, a marked reduction in new growth of the plants treatedwith compounds of Tables 4 and 5 is observed (less than 20% of the newgrowth of untreated control plants), without damage being caused to thetest plants.

EXAMPLE 12 Growth regulation of soybeans

Soybeans of the "Hark" variety are sown in plastic containers in anearth/peat/sand mixture (6:3:1). The containers are put into a climaticchamber and the plants develop to the 5-6 trefoil leaf stage after about5 weeks by optimum control of temperature, light, fertiliser addition,and watering. The plants are then sprayed with an aqueous mixture of acompound of formula I until thoroughly wetted. The concentrationcorresponds to up to 2000 g a.i. per hectare. Evaluation is made about 5weeks after application of the test compound. Compared with untreatedcontrol plants, there is a marked increase in the number and weight ofthe siliquae on plants which have been treated with compounds of Tables4 and 5.

EXAMPLE 13 Growth inhibition of cereals

Summer barley (Hordeum vulgare) and summer rye (Secale) are sown insterilised soil in plastic beakers in a greenhouse and watered asrequired. The cereal shoots are treated about 21 days after sowing withan aqueous spray mixture of a compound of formula I. The concentrationcorresponds to up to 3000 g of active ingredient per hectare. Evaluationof the growth of the cereals is made 21 days after application. Acomparison with untreated controls shows that the new growth of treatedcereal plants is reduced (60-90% of the controls) and that the diameterof the stalks has in some cases increased.

EXAMPLE 14 Growth inhibition of grasses

Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina,Dactylis glomerate and Cynodon dactylon are sown in plastic dishesfilled with an earth/peat/sand mixture (6:3:1), in a greenhouse, andwatered as required. The emergent grasses are cut back weekly to aheight of 4 cm, and about 50 days after sowing and 1 day after the lastcut are sprayed with an aqueous spray mixture of a compound of formulaI. The concentration of test compound corresponds to a rate ofapplication of up to 3000 g a.i. per hectare. The growth of the grassesis evaluated 21 days after application. The test compounds of Tables 4and 5 effect a reduction in new growth in the range of 10-30% incomparison with untreated controls.

What is claimed is:
 1. A 2-acyl-1,3-cyclohexanedione, or an oxime etherthereof, of formula I ##STR41## wherein A is a 2- to 7-membered alkylenebridge, or a 3- to 7-membered alkenylene bridge which may be mono- orpolyunsaturated,n is 0, 1 or 2, R₁ is C₁ -C₄ alkyl or benzyl, R₂ is C₁-C₆ alkyl which is unsubstituted or substituted by halogen, C₁ -C₄alkoxy or C₁ -C₄ alkylthio; or is C₃ -C₆ cycloalkyl; or phenyl, benzylor phenylethyl, the phenyl ring of each of which may be substituted byhalogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄haloalkyl, C₁ -C₄ haloalkoxy, cyano or nitro, X is oxygen or a radical--NOR₃, and R₃ is C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₃ -C₆ alkenyl, C₃ -C₆haloalkenyl or C₃ -C₆ alkynyland the metal and quaternary ammonium saltsof these compounds.
 2. An acylcyclohexanedione according to claim 1 offormula Ia ##STR42## wherein A is a 2- to 7-membered alkylene bridge,nis 0, 1 or 2, R₁ is C₁ -C₄ alkyl or benzyl, R₂ is C₁ -C₆ alkyl which isunsubstituted or substituted by halogen, C₁ -C₄ alkoxy or C₁ -C₄alkylthio; or is C₃ -C₆ cycloalkyl; or phenyl, benzyl or phenylethyl,the phenyl ring of each of which may be substituted by halogen, C₁ -C₄alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ haloalkyl, C₁ -C₄haloalkoxy, cyano or nitro.
 3. An acylcyclohexanedione according toclaim 2 of the formula Ia, wherein A is the ethylene bridge, n is 0, R₁is methyl or ethyl and R₂ is ethyl or n-propyl. 4.5-(1-Methylthiocyclobutan-1-yl)-2-(2,4-dichlorobenzoyl)cyclohexane-1,3-dioneaccording to claim
 1. 5.5-(1-Methylthiocyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dioneaccording to claim
 1. 6.5-(1-Methylthiocyclobutan-1-yl)-2-cyclopropylcarbonylcyclohexane-1,3-dioneaccording to claim 1.7.5-(1-Methylthiocyclobutan-1-yl)-2-(2,3-dichlorobenzoyl)cyclohexane-1,3-dioneaccording to claim
 1. 8.5-(1-Methylsulfonylcyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dioneaccording to claim
 1. 9.5-(1-Methylthiocyclopropan-1-yl)-2-n-butyrylcyclohexane-1,3-dioneaccording to claim
 1. 10.5-(1-Methylthiocyclopropan-1-yl)-2-propionylcyclohexane-1,3-dioneaccording to claim
 1. 11.5-(1-Ethylthiocyclopropan-1-yl)-2-propionylcyclohexane-1,3-dioneaccording to claim
 1. 12. An acylcyclohexanedione oxime ether accordingto claim 1 of formula Ib ##STR43## wherein A is a 2- to 7-memberedalkylene bridge,n is 0, 1 or 2, R₁ is C₁ -C₄ alkyl or benzyl, R₂ is C₁-C₆ alkyl which is unsubstituted or substituted by halogen, C₁ -C₄alkoxy or C₁ -C₄ alkylthio, and R₃ is C₁ -C₆ alkyl, C₃ -C₆ haloalkyl, C₃-C₆ alkenyl, C₃ -C₆ haloalkenyl or C₃ -C₆ alkynyland the metal andquaternary ammonium salts of these compounds.
 13. Anacylcyclohexanedione oxime ether according to claim 12 of formula Ib,wherein A is the ethylene bridge, n is 0, R₁ is methyl or ethyl, R₂ isethyl or n-propyl and R₃ is cis- or trans-3-chloroallyl. 14.5-(1-Methylthiocyclopentan-1-yl)-2-(1'-ethoximinobutyryl)cyclohexane-1,3-dioneaccording to claim
 1. 15.5-(1-Methylthiocyclobutan-1-yl)-2-(1'-ethoxyiminobutyryl)cyclohexane-1,3-dioneaccording to claim
 1. 16.5-(1-Methylthiocyclohexan-1-yl)-2-(1-ethoximinobutyryl)cyclohexane-1,3-dioneaccording to claim
 1. 17.5-(1-Methylthiocyclobutan-1-yl)-2-(1'-allyloxyiminobutyryl)cyclohexane-1,3-dioneaccording to claim
 1. 18.5-(1-Methylthiocyclopropan-1-yl)-2-(1-ethoximinobutyryl)cyclohexane-1,3-dioneaccording to claim
 1. 19.5-(1-Methylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloximino)-n-butyryl]cyclohexane-1,3-dioneaccording to claim
 1. 20.5-(1-Methylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloximino)propionyl]cyclohexane-1,3-dioneaccording to claim
 1. 21.5-(1-Methylthiocyclopropan-1yl)-2-[1-(cis-3-chloroallyloximino)propionyl]cyclohexane-1,3-dioneaccording to claim
 1. 22.5-(1-Ethylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloximino)propionyl]cyclohexane-1,3-dioneaccording to claim
 1. 23.5-(1-Ethylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloximino)-n-butyryl]cyclohexane-1,3-dioneaccording to claim
 1. 24. A salt of a2-acyl-1,3-cyclohexanedione-oxime-ether of the formula Ic ##STR44##wherein A, n, R₁, R₂ and R₃ have the meaning given in claim 1 andM.sup.⊕ is the ion-equivalent of a metal or a quaternary ammonium ion,according to claim
 1. 25. Sodium2-[1-(3-trans-chlorallyloxyamino)-propylidene-3-oxo-5-(1-methylthio-1-cyclopropyl)-cyclohex-1-en-1-olateaccording to claim
 1. 26. A herbicidal and plant growth regulatingcomposition which contains, as active ingredient, anacylcyclohexandione, or an oxime ether thereof, of formula I accordingto claim 1, together with carriers and/or other adjuvants.
 27. A methodof controlling undesired plant growth, which method comprises applyingto the plants or to the locus thereof a herbicidally effective amount ofa compound according to claim
 1. 28. A method of inhibiting the growthof grasses, which method comprises applying to said grasses or to thelocus thereof a plant growth inhibiting amount of a compound accordingto claim
 1. 29. A method of selectively controlling weeds pre- orpostemergence in crops of useful plants, which method comprises treatingthe crop area with a herbicidally effective amount of a compoundaccording to claim
 1. 30. A method of selectively controlling grassweeds pre- or post-emergence in crops of useful plants, which methodcomprises treating said the crop area thereof with an effective amountof a compound according to claim
 1. 31. A method of regulating plantgrowth, which method comprises treating plants, parts of plants or seedswith a growth-regulatingly effective amount of a compound according toclaim 1.